Herbicidal antidote compositions with substituted oxazolidines and thiazolidines

ABSTRACT

Herbicidal compositions comprising an active herbicidal compound and antidote therefor and the methods of use; the antidote compound corresponds to substituted oxazolidines and thiazolidines having the formula   &lt;IMAGE&gt;   in which X is oxygen or sulfur; R is haloalkyl, alkyl or alkylthio; and R1, R2, R3, R4, R5 and R6 are independently selected from the group consisting of hydrogen, lower alkyl, alkoxyalkyl and lower alkylol.

CROSS REFERENCE TO RELATED APPLICATION

This is a division, of application Ser. No. 356,547 filed May 2, 1973now U.S. Pat. No. 3,989,503 issued Nov. 2, 1976 which is acontinuation-in-part of Ser. No. 297,561, filed Oct. 13, 1972, nowabandoned which is a continuation-in-part of Ser. No. 208,041, filedDec. 9, 1971 now abandoned which is a continuation-in-part of Ser. No.134,868, filed Apr. 16, 1971, now abandoned.

BACKGROUND OF THE INVENTION

Among the many herbicidal compounds commercially available, thethiocarbamates alone or admixed with other herbicides, such as thetriazines, have reached a relatively high degree of commercial success.These herbicides are immediately toxic to a large number of weed pestsat different concentrations varying with the resistance of the weedpests. Some examples of these compounds are described and claimed inU.S. Pat. Nos. 2,913,327, 3,037,853, 3,175,897, 3,185,720, 3,198,786 and3,582,314. It has been found in practice that the use of thesethiocarbamates as herbicides on crops sometimes causes serious injuriesto the crop plant. When used in the recommended amounts in the soil tocontrol many broadleaf weeds and grasses, serious malformation andstunting of the crop plants result. This abnormal growth in the cropplants results in loss of crop yield. Previous attempts to overcome thisproblem involves the treatment of the crop seed with certainantagonistic agents prior to planting, see U.S. Pat. Nos. 3,131,509 and3,564,768. These antagonistic agents have not been notably successful.The aforementioned patent specifically exemplifies the treatment ofseeds employing compounds of a different chemical class not suggestiveof the present invention.

Other preferred herbicidal compounds whose effect can be modified by theinstant compounds include the acetanilides, such as2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide and the urea-typeherbicides, such as 3-(3,4-dichlorophenyl)-1,1-dimethylurea.

DESCRIPTION OF THE INVENTION

It has been discovered that plants can be protected against injury bythe thiolcarbamate-type herbicides, alone or mixed with other compoundsand/or the tolerance of the plants can be substantially increased to theactive compounds of the above-noted U.S. Patents by adding to the soilan antidote compound corresponding to the following formula: ##STR2## inwhich X is oxygen or sulfur; R is haloalkyl, alkyl or alkylthio; and R₁,R₂, R₃, R₄, R₅ and R₆ are independently selected from the groupconsisting of hydrogen, lower alkyl, alkoxyalkyl and lower alkylol.

In the above description, the following embodiments are intended for thevarious substituent groups: for R, haloalkyl and alkyl preferablyincludes, unless otherwise provided for, those members which containfrom 1 to 10 carbon atoms, inclusive, in both straight chain andbranched chain configurations, and the term halo includes chloro andbromo as mono, di, tri, tetra and per substitutions. As exemplary of thealkyl portion within the preferred embodiment are the following: methyl,ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, 1,1-dimethylbutyl,amyl, isoamyl, 2,4,4-trimethylpentyl, n-hexyl, isohexyl, n-heptyl,n-octyl, isooctyl, nonyl, and decyl. The term alkylthio preferablyincludes those members which contain from 1 to 4 carbon atoms,inclusive, for example, methylthio, ethylthio, n-propylthio,isopropylthio, n-butylthio, t-butylthio, and the like. For R₁ R₂, R₃,R₄, R₅ and R₆, the term lower alkyl preferably includes, unlessotherwise provided for, those members which contain from 1 to 4 carbonatoms, inclusive, for example, methyl, ethyl, n-propyl, isopropyl,n-butyl, sec.-butyl, tert.-butyl, and the like. The term alkoxyalkylpreferably includes those members having a total of 2 to 4 carbon atoms,inclusive for example, methoxymethyl, methoxyethyl, ethoxyethyl,ethoxymethyl and the like. The term lower alkylol preferably includesthose members having 1 to 4 carbon atoms, inclusive for example,methylol, ethylol, propylol and butylol.

As an alternative mode of action, the compounds of this invention mayinterfere with the normal herbicidal action of the thiocarbamate-typeand other herbicides to render them selective in their action. Whichevermode of action is present, the corresponding beneficial and desirableeffect is the continued herbicidal effect of the thiocarbamate with theaccompanying decreased herbicidal effect on desired crop species. Thisadvantage and utility will become more apparent hereinafter.

Therefore, the terms herbicide, antidote or anitdotal amount, is meantto describe that effect which tends to counteract the normal injuriousherbicidal response that the herbicide might otherwise produce. Whetherit is to be termed a remedy, interferant, protectant, or the like, willdepend upon the exact mode of action. The mode of action is varied, butthe effect, which is desirable, is the result of the method of treatingthe soil in which a crop is planted. Hitherto, there have been nosystems which have been satisfactory for this purpose.

The compounds of this invention represented by the above formula can beprepared by several different procedures depending upon the startingmaterials.

The oxazolidine and thiazolidine intermediates were prepared by thecondensation of the amino alcohol or mercaptan with a suitable aldehydeor ketone in boiling benzene with the continuous separation of water.This method is described by Bergmann et al., JACS 75 358 (1953).Usually, the oxazolidines and thiazolidines intermediates were pureenough to be used directly without further purification. Aliquots ofthese solutions were then used to prepare the compounds of thisinvention.

The appropriate intermediate was reacted with an acid chloride in thepresence of a hydrogen chloride acceptor, such as triethylamine, toprepare the desired compound. Workup and purification proceduresinvolved standard methods of extration, distillation or crystallization.

The compounds of the present invention and their preparation are moreparticularly illustrated by the following examples. Following theexamples of preparation is a table of compounds which are preparedaccording to the procedures described herein. Compound numbers have beenassigned to them and are used for identification throughout the balanceof the specification.

EXAMPLE IA Preparation of 2,2-dimethyl-3-dichloroacetyl oxazolidine

Five and one-tenth (5.1g.) grams of 2,2-dimethyl oxazolidine dissolvedin 50 ml. of benzene was treated with 5.5 g. of triethylamine and 7.4 g.of dichloroacetyl chloride was added dropwise with stirring and coolingin an ice bath. The mixture was poured into water, the benzene solutionseparated, dried over anhydrous magnesium sulfate and the solventstripped under vacuum. The product was a waxy solid which had a meltingpoint of 113°-115° C. on recrystallization from diethyl ether.

EXAMPLE IB ##STR3##

15 g. of acetone and 12.2 g. of ethanol amine were combined in 150 ml.of benzene and refluxed until no additional water came over. Theresulting solution was examined and found to contain2,2-dimethyl-1,3-oxazolidine. A quarter of the benzene solution (0.05mole) was reacted with 7.4 g. of dichloroacetyl chloride and 5.5 g. oftriethylamine, washed with water, dried and stripped under vacuum togive a light tan solid. A portion was recrystallized from ether giving awhite product.

EXAMPLE II Preparation of 2,2,5-trimethyl-3-dichloroacetyl oxazolidine

Eighteen (18) milliliters of a benzene solution containing 4.6 g. of2,2,5-trimethyl oxazolidine was added to 25 ml. of benzene and 4.5 g. oftriethylamine. Five and nine-tenths (5.9 g.) grams of dichloroacetylchloride was added dropwise with stirring and cooling in an ice bath.When reaction was complete the mixture was poured into water and thebenzene layer separated, dried over anhydrous magnesium sulfate and thebenzene removed under vacuum. Yield was 7.7 g. of an oil, n_(D) ³⁰ =1.4950.

EXAMPLE III Preparation of 2,2-dimethyl-3-dichloroacetyl thiazolidine

Four and seven-tenths (4.7 g.) grams of 2,2-dimethyl thiazolidine and4.5 g. of triethylamine were dissolved in 50 ml. of methylene chlorideand 5.9 g. of dichloroacetyl chloride was added dropwise with stirring.The mixture was cooled in a water bath at room temperature.

When reaction was complete, the mixture was poured into water and thesolvent layer separated, dried over anhydrous magnesium sulfate, and thesolvent removed under vacuum. Yield was 3.6 g. of a waxy solid.Recrystallization of another sample from diethyl ether gave a whitesolid, m.p. 109°-111° C.

EXAMPLE IV Preparation of2,2,5-trimethyl-3(2,',3'-dibromopropionyl)oxazolidine

Fourteen (14 ml.) milliliters of a benzene solution containing 3.5 g. of2,2,5-trimethyl oxazolidine was added to 25 ml. of benzene and 3.5 g. oftriethylamine. Seven and one-half (7.5 g.) grams of 2,3-dibromopropionylchloride was added dropwise with stirring and cooling in an ice bath.When reaction was complete, the mixture was poured into water andbenzene layer separated, dried over anhydrous magnesium sulfate and thesolvent stripped under vacuum. The yield was 5.7 g. of an oil, n_(D) ³⁰= 1.5060.

EXAMPLE V Preparation of 2,2-dimethyl-3-dibromoacetyl thiazolidine

To a mixture of 3.5 g. of 2,2-dimethyl thiazolidine, 50 ml. of benzeneand 7.1 g. of dibromoacetyl chloride mixed in an ice bath was added 3.1g. of triethylamine dropwise with stirring and continued cooling. Whenreaction was complete, the mixture was poured into water and the benzenelayer separated, dried over magnesium sulfate and the benzene removedunder vacuum. Yield was 8.5 g. of a dark oil.

EXAMPLE VI Preparation of 2-ethyl-3-S-ethylthiocarbonyl oxazolidine

Sixteen and one half (16.5 ml.) milliliters of a benzene solution of2-ethyl oxazolidine was added to 50 ml. of benzene and 4.1 g. oftriethylamine. Five (5 g.) grams of ethyl chlorothiolformate was addeddropwise with stirring and cooling in an ice bath. The mixture waspoured into water and the benzene solution separated, dried overanhydrous magnesium sulfate and the benzene stripped under vacuum. Yieldwas 5.6 g. of an oil, n_(D) ³⁰ = 1.5130.

EXAMPLE VII Preparation of 2,2-dimethyl-3-heptanoyl oxazolidine

Sixteen and one-half (16.5 ml.) milliliters of a benzene solutioncontaining 4.6 g. of 2,2-dimethyl oxazolidine was added to 50 ml. ofbenzene and 4.1 g. of triethylamine. To this mixture 6 g. of n-heptanoylchloride was added dropwise with stirring and cooling in an ice bath.The mixture was poured into water and the benzene layer extracted, driedover magnesium sulfate and the benzene removed under vacuum. Yield was7.5 g. of an oil, n_(D) ³⁰ = 1.4598.

                                      TABLE I                                     __________________________________________________________________________     ##STR4##                                                                     COMPOUND                                            m.p. ° C.          NUMBER   R          R.sub.1                                                                              R.sub.2                                                                            R.sub.3                                                                           R.sub.4                                                                             R.sub.5                                                                           R.sub.6                                                                          X  or n.sub.D.sup.30         __________________________________________________________________________    1        CHCl.sub.2 CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  O  116-118                   2        CH.sub.2 Cl                                                                              CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  O  1.4932                    3        CBr.sub.3  CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  O  1.5560                    4        CBr.sub.3  CH.sub.3                                                                             CH.sub.3                                                                           H   H     CH.sub.3                                                                          H  O  Glass                     5        CH.sub.2 Cl                                                                              CH.sub.3                                                                             CH.sub.3                                                                           H   H     CH.sub.3                                                                          H  O  1.4842                    6        CHCl.sub.2 CH.sub.3                                                                             CH.sub.3                                                                           H   H     CH.sub.3                                                                          H  O  1.4950                    7        CH.sub.2 Cl                                                                              CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H     H   H  O  1.4900                    8        CHCl.sub.2 CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H     H   H  O  1.4950                    9        CCl.sub.3  CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H     H   H  O  1.4970                    10       CBr.sub.3  CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H     H   H  O  1.5428                    11       CH.sub.3 CHBr                                                                            CH.sub.3                                                                             CH.sub.3                                                                           H   H     CH.sub.3                                                                          H  O  1.4993                    12       CH.sub.3 CHBr                                                                            CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H     H   H  O  1.4993                    13       CH.sub.2 Cl                                                                              CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H     H   H  O  1.4928                    14       CHCl.sub.2 CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H     H   H  O  1.4982                    15       CCl.sub.3  CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H     H   H  O  1.5034                    16       CH.sub.3 CHBr                                                                            CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H     H   H  O  1.5058                    17       CBr.sub.3  CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H     H   H  O  95-97                     18       CH.sub.2 Br                                                                              CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H     H   H  O  1.5097                    19       CH.sub.2 Br                                                                              CH.sub.3                                                                             CH.sub.3                                                                           H   H     CH.sub.3                                                                          H  O  1.5020                    20       CH.sub.2 Br                                                                              CH.sub.3                                                                             CH.sub. 3                                                                          C.sub.2 H.sub.5                                                                   H     H   H  O  1.5048                    21       CH.sub.3 (CHBr).sub.4                                                                    CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  O  1.5658                    22       CH.sub.2 Cl                                                                              CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                            H   H  O  1.4843                    23       CHCl.sub.2 CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                            H   H  O  120-123                   24       CCl.sub.2  CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                            H   H  O  1.5031                    25       CH.sub.2 Br                                                                              CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                            H   H  O  1.5116                    26       CH.sub.3 CHBr                                                                            CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                            H   H  O  1.5140                    27       CBr.sub.3  CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                            H   H  O  1.5610                    28       ClCH.sub.2 CH.sub.2                                                                      CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  O  1.4538                    29       CHCl.sub.2 C.sub.2 H.sub.5                                                                      H    H   H     H   H  S  1.5458                    30       CHCl.sub.2 CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  S  109-111                   31       CH.sub.2 BrCHBr                                                                          CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H     H   H  O  1.5170                    32       CH.sub.2 BrCHBr                                                                          CH.sub.3                                                                             CH.sub.3                                                                           H   H     CH.sub.3                                                                          H  O  1.5060                    33       CH.sub.2 BrCHBr                                                                          CH.sub.3                                                                             CH.sub. 3                                                                          C.sub.2 H.sub.5                                                                   H     H   H  O  1.5083                    34       CH.sub.2 BrCHBr                                                                          CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  O  1.5178                    35       CH.sub.2 BrCHBr                                                                          CH.sub.3                                                                             t-C.sub.4 H.sub.9                                                                  H   H     H   H  O  1.5165                    36       CHCl.sub.2 CH.sub.3                                                                             t-C.sub.4 H.sub.9                                                                  H   H     H   H  O  1.4949                    37       CBr.sub.3  CH.sub.3                                                                             t-C.sub.4 H.sub.9                                                                  H   H     H   H  O  1.5431                    38       CHCl.sub.2 H      H    CH.sub.3                                                                          CH.sub.3                                                                            H   H  O  1.5033                    39       CHCl.sub.2 CH.sub.3 OCH.sub.2                                                                   H    H   H     H   H  O  1.5132                    40       CHCl.sub.2 C.sub.3 H.sub.7                                                                      H    H   H     H   H  O  1.4988                    41       CHCl.sub.2 C.sub.2 H.sub.5                                                                      H    H   H     H   H  O  1.5126                    42       CHBr.sub.2 C.sub.2 H.sub.5                                                                      H    H   H     H   H  O  1.5750                    43       CBr.sub.3  C.sub.2 H.sub.5                                                                      H    H   H     H   H  O  1.5610                    44       CH.sub.2 Br                                                                              C.sub.2 H.sub.5                                                                      H    H   H     H   H  O  1.5200                    45       CH.sub.3 CHBr                                                                            C.sub.2 H.sub.5                                                                      H    H   H     H   H  O  1.5140                    46       (CH.sub.3).sub.2 CBr                                                                     C.sub.2 H.sub.5                                                                      H    H   H     H   H  O  1.4958                    47       CH.sub.2 BrCHBr                                                                          C.sub.2 H.sub.5                                                                      H    H   H     H   H  O  1.5273                    48       CH.sub.2 Cl                                                                              C.sub.2 H.sub.5                                                                      H    H   H     H   H  O  1.5020                    49       CHCl.sub.2 C.sub.2 H.sub.5                                                                      H    H   H     CH.sub.3                                                                          H  O  1.4955                    50       CH.sub.2 Cl                                                                              C.sub.2 H.sub.5                                                                      H    H   H     CH.sub.3                                                                          H  O  1.4890                    51       CH.sub.2 Br                                                                              C.sub.2 H.sub.5                                                                      H    H   H     CH.sub.3                                                                          H  O  1.5064                    52       CHBr.sub.2 C.sub.2 H.sub.5                                                                      H    H   H     CH.sub.3                                                                          H  O  Glass                     53       CBr.sub.3  C.sub.2 H.sub.5                                                                      H    H   H     CH.sub.3                                                                          H  O  Glass                     54       CH.sub.3 CHBr                                                                            C.sub.2 H.sub.5                                                                      H    H   H     CH.sub.3                                                                          H  O  1.4978                    55       CH.sub.2 BrCHBr                                                                          C.sub.2 H.sub.5                                                                      H    H   H     CH.sub.3                                                                          H  O  1.5138                    56       (CH.sub.3).sub.2 CBr                                                                     C.sub.2 H.sub.5                                                                      H    H   H     CH.sub.3                                                                          H  O  1.4851                    57       CHCl.sub.2 H      H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.5030                    58       CHBr.sub.2 H      H    C.sub.2 H.sub.5                                                                   H     H   H  O  Dark liquid               59       CBr.sub.3  H      H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.5531                    60       CH.sub.2 Br                                                                              H      H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.5173                    61       CH.sub.3 CHBr                                                                            H      H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.5076                    62       (CH.sub.3).sub.2 CBr                                                                     H      H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.4852                    63       CH.sub.2 BrCHBr                                                                          H      H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.5249                    64       CCl.sub.3  H      H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.5048                    65       CH.sub.2 Cl                                                                              H      H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.4998                    66       CHCl.sub.2 CH.sub.3                                                                             H    H   H     H   H  O  1.5112                    67       CCl.sub.3  CH.sub.3                                                                             H    H   H     H   H  O  1.5148                    68       CH.sub.2 Cl                                                                              CH.sub.3                                                                             H    H   H     H   H  O  1.5077                    69       CH.sub.2 Br                                                                              CH.sub.3                                                                             H    H   H     H   H  O  1.5263                    70       CHBr.sub.2 CH.sub.3                                                                             H    H   H     H   H  O  1.5471                    71       CBr.sub.3  CH.sub.3                                                                             H    H   H     H   H  O  Dark liquid               72       CH.sub.2 BrCHBr                                                                          CH.sub.3                                                                             H    H   H     H   H  O  1.5280                    73       CH.sub.3 CHBr                                                                            CH.sub.3                                                                             H    H   H     H   H  O  1.5162                    74       (CH.sub.3).sub.2 CBr                                                                     CH.sub.3                                                                             H    H   H     H   H  O  1.5013                    75       CHCl.sub.2 CH.sub.3                                                                             H    H   H     CH.sub.3                                                                          H  O  1.4983                    76       CCl.sub.3  CH.sub.3                                                                             H    H   H     CH.sub.3                                                                          H  O  1.4990                    77       CH.sub.2 Cl                                                                              CH.sub.3                                                                             H    H   H     CH.sub.3                                                                          H  O  1.4958                    78       CHBr.sub.2 CH.sub.3                                                                             H    H   H     CH.sub.3                                                                          H  O  Dark liquid               79       CH.sub.3 CHBr                                                                            CH.sub.3                                                                             H    H   H     CH.sub.3                                                                          H  O  1.5083                    80       CHBr.sub. 2                                                                              C.sub.2 H.sub.5                                                                      H    H   H     H   H  S  1.5782                    81       CH.sub.2 BrCHBr                                                                          C.sub.2 H.sub.5                                                                      H    H   H     H   H  S  1.5650                    82       CCl.sub.3  CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  S  1.5638                    83       CHBr.sub.2 CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  S  Dark liquid               84       CH.sub.3 CHBr                                                                            CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  S  1.5520                    85       CHCl.sub.2 H      H    H   H     H   H  S  75-77                     86       CHCl.sub.2 CH.sub.3                                                                             i-C.sub.3 H.sub.7                                                                  H   H     H   H  O  1.4960                    87       CHCl.sub.2 CH.sub.3                                                                             CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.2 OH                                                                         H   H  O  1.4960                    88       CH.sub.2 BrC(CH.sub.3)Br                                                                 C.sub.2 H.sub.5                                                                      H    H   H     H   H  O  1.5318                    89       CH.sub.2 BrC(CH.sub.3)Br                                                                 C.sub.2 H.sub.5                                                                      H    H   H     CH.sub.3                                                                          H  O  1.5225                    90       CH.sub.2 BrC(CH.sub.3)Br                                                                 CH.sub.3                                                                             H    H   H     CH.sub.3                                                                          H  O  1.5210                    91       CHCl.sub.2 C.sub.2 H.sub.5                                                                      H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.4947                    92       C.sub.2 H.sub.5 S                                                                        H      H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.4998                    93       C.sub.2 H.sub.5 S                                                                        CH.sub.3                                                                             H    H   H     CH.sub.3                                                                          H  O  1.4965                    94       C.sub.2 H.sub.5 S                                                                        C.sub.2 H.sub.5                                                                      H    H   H     CH.sub.3                                                                          H  O  1.4973                    95       C.sub.2 H.sub.5 S                                                                        C.sub.2 H.sub.5                                                                      H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.4928                    96       CCl.sub.3  C.sub.2 H.sub.5                                                                      H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.4937                    97       CH.sub.2 BrCHBr                                                                          C.sub.2 H.sub.5                                                                      H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.5198                    98       CH.sub.2 BrC(CH.sub.3)Br                                                                 C.sub.2 H.sub.5                                                                      H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.5202                    99       CH.sub.2 BrCH.sub.2                                                                      C.sub.2 H.sub.5                                                                      H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.4920                    100      CHCl.sub.2 CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.4960                    101      C.sub.3 H.sub.7 S                                                                        CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.4900                    102      i-C.sub.3 H.sub.7 S                                                                      CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.4875                    103      CCl.sub.3  CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.4990                    104      CH.sub.2 Br                                                                              CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.5070                    105      CH.sub.2 BrCHBr                                                                          CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.5168                    106      CH.sub.2 BrC(CH.sub.3)Br                                                                 CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.5160                    107      CH.sub.2 BrCH.sub.2                                                                      CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.4950                    108      C.sub.4 H.sub.9 S                                                                        CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.4928                    109      C.sub.4 H.sub.9 S                                                                        C.sub.2 H.sub.5                                                                      H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.4880                    110      CH.sub.3 S CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                   H     H   H  O  1.4980                    111      C.sub.6 H.sub.13                                                                         CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  O  1.4598                    112      CH.sub.3 S CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H     H   H  O  1.4913                    113      n-C.sub.3 H.sub.7 S                                                                      CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H     H   H  O  1.4858                    114      i-C.sub.3 H.sub.7 S                                                                      CH.sub.3                                                                             CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H     H   H  O  1.4828                    115      CH.sub.2 BrCH.sub.2                                                                      CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  O  1.4912                    116      CH.sub.2 BrCHBr                                                                          H      H    CH.sub.3                                                                          CH.sub.3                                                                            H   H  O  1.5221                    117      CH.sub.2 BrCH.sub.2                                                                      CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  S  1.5263                    118      CH.sub.2 BrCHBr                                                                          CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  S  1.5573                    119      CH.sub.2 BrCH.sub.2                                                                      H      H    CH.sub.3                                                                          CH.sub.3                                                                            H   H  O  1.4890                    120      CH.sub.2 Br                                                                              H      H    H   H     H   H  S  1.6032                    121      CH.sub.3 CHBr                                                                            H      H    H   H     H   H  S  1.5720                    122      CH.sub.2 BrCH.sub.2                                                                      H      H    H   H     H   H  S  1.5629                    123      CH.sub.2 BrCHBr                                                                          H      H    H   H     H   H  S  1.5742                    124      CH.sub.3 C(CH.sub.3)Br                                                                   H      H    H   H     H   H  S  1.5420                    125      CH.sub.2 ClCH.sub.2                                                                      H      H    H   H     H   H  S  1.5475                    126      BrCH.sub.2 (CH.sub.2).sub.8 CH.sub.2                                                     CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  O  1.4898                    127      ClCH.sub.2 CH.sub.2 CH.sub.2                                                             CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  O  1.4880                    128      ClCH.sub.2 CH.sub.2 CH.sub.2                                                             CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  S  1.5183                    129      CH.sub.3 CHClCH.sub.2                                                                    CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  O  1.4896                    130      CH.sub.3 CHClCH.sub.2                                                                    CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  O  1.5115                    131      CH.sub.3 CHClCH.sub.2                                                                    CH.sub.3                                                                             CH.sub.3                                                                           H   H     CH.sub.3                                                                          H  O  1.4701                    132      C.sub.2 H.sub.5 CHBr                                                                     CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  O  1.5020                    133      C.sub.2 H.sub.5 CHBr                                                                     CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  S  1.5288                    134      C.sub.2 H.sub.5 CHBr                                                                     CH.sub.3                                                                             CH.sub.3                                                                           H   H     CH.sub.3                                                                          H  O  1.4900                    135      C.sub.3 H.sub.7 CHBr                                                                     CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  O  1.4972                    136      C.sub.3 H.sub.7 CHBr                                                                     CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  S  1.5220                    137      C.sub.3 H.sub.7 CHBr                                                                     CH.sub.3                                                                             CH.sub.3                                                                           H   H     CH.sub.3                                                                          H  O  1.4870                    138      CH.sub.2 ClCH.sub.2 CH.sub.2                                                             CH.sub.3                                                                             CH.sub.3                                                                           H   H     CH.sub.3                                                                          H  O  1.4747                    139      CH.sub.2 Br(CH.sub.2).sub.4                                                              CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  O  1.4970                    140      CH.sub.2 Br(CH.sub.2).sub.4                                                              CH.sub.3                                                                             CH.sub.3                                                                           H   H     CH.sub.3                                                                          H  O  1.4886                    141      CH.sub.2 Br(CH.sub.2).sub.4                                                              CH.sub.3                                                                             CH.sub.3                                                                           H   H     H   H  S  1.5249                    142      CHCl.sub.2 H      H    H   H     H   H  O  1.5136                    143      CH.sub.2 BrCBr(CH.sub.3)                                                                 H      H    H   H     H   H  S  Semi-solid                144      CH.sub.2 Cl                                                                              H      H    H   H     H   H  S  1.5540                    145      CHCl.sub.2 CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H     H   H  S  1.5443                    146      CH.sub.3 CHBr                                                                            CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H     H   H  S  1.4327                    147      CH.sub.2 BrCH.sub.2                                                                      CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H     H   H  S  1.4293                    148      CH.sub.2 Cl                                                                              CH.sub.3                                                                             C.sub.2 H.sub.5                                                                    H   H     H   H  S  1.5279                    __________________________________________________________________________

the compounds of this invention were employed in effective herbicidalantidote compositions comprising thiocarbamates in combination withantidote compounds described hereinabove. They were tested in thefollowing manner.

CORN SEED TREATMENT TEST

Small flats were filled with Felton loamy sand soil. Soil incorporatedherbicides were applied at this time. The soil from each flat was placedinto a five-gallon cement mixer where the soil was mixed as theherbicides were applied using a predetermined amount of a stock solutioncontaining 936 mg. of 75.5% active ingredient to 100 ml. of water. Oneml. of stock solution was applied to the soil in a volumetric pipet foreach pound of herbicide desired. One ml. of stock solution contained 7mg. of herbicide which equals one pound per acre when applied to thesoil in the flats. After the herbicide incorporation, the soil wasplaced back into the flats.

Flats of herbicide-treated and untreated soil were then ready to beplanted. A pint sample of soil was removed from each flat and placednext to each flat for later use in covering up the seeds. The soil wasleveled and rows one-half inch deep were made for planting seeds.Alternating rows of treated and untreated crop seeds were sown. In eachtest, six PAG 344T field corn seeds were planted in each row. Rows wereapproximately 1-1/2 inches apart in the flat. Seed were treated byeither (1) placing 50 mg. of the antidote compound with 10 grams of cornseed (0.5% w/w) in a suitable container and shaking them until the seedswere uniformly covered with the compound, or (2) preparing a stocksolution by dissolving 50 mg. of the antidote compound in 5 ml. ofacetone, then using 0.5 ml. of the stock solution to treat 10 g. of cornseed (0.05% w/w). Antidote compounds were also applied as liquidslurries and powders or dusts. In some cases, acetone was used todissolve powdered or solid compounds so they could be more effectivelyapplied to the seeds.

After the flats were seeded, they were covered with the one pint of soilwhich had been removed just prior to planting. Flats were placed ongreenhouse benches where temperatures ranged from 70°-90° F. Flats werewatered by sprinkling as needed to assure good plant growth. Per centcontrol ratings were taken two, three and four weeks after thetreatments were applied.

In each test, the herbicide was applied alone, in combination with theseed protectant, and the seed protectant was applied alone to check forphytotoxicity. The untreated adjacent row was employed to observe anybeneficial lateral movement of the antidote compound through the soil.The degree of the effect was noted by comparison with the control. Theresults of these tests are tabulated in Table II.

                  TABLE II                                                        ______________________________________                                        Per Cent Injury to Corn from EPTC*                                            Seed Treatment Test                                                                         Per Cent Injury, 2 weeks                                                        Treated     Untreated                                         COMPOUND        Seed        Seed                                              NUMBER          (0.05% w/w) Adjacent Row                                      ______________________________________                                         1              0           0                                                  1**            5           30                                                 2              70          80                                                 3**            40          60                                                 4              10          50                                                 5              30          60                                                 6              0           0                                                  7              40          55                                                 8              0           15                                                 9              10          55                                                10              20          60                                                11              30          50                                                12              10          40                                                13              50          70                                                14              0           20                                                15              20          50                                                16              10          55                                                17              30          50                                                18              20          50                                                19              40          50                                                20              20          60                                                21              50          50                                                22              60          60                                                23              50          60                                                24              20          60                                                25              20          70                                                26              20          60                                                27              20          60                                                28              60          70                                                29              0           5                                                 30              20          5                                                 142***          10          75                                                EPTC 6E Untreated Seed                                                                        --          70                                                                            80 (4 weeks)                                      ______________________________________                                         * = S-ethyl dipropylthiocarbamate 6E: 6 lb/A preplant incorporated            ** = Seed treatment 0.01% w/w                                                 *** = Seed treatment 0.5% w/w                                            

With 2-chloro-2',6'-diethyl-N-methoxymethyl)acetanilide at 2 lb/A as aseed treatment, 0.5%, Compound No. 145 gave 100% protection to sorghum(Milo).

PROCEDURE: MULTICROP ANTIDOTE SCREEN

Plastic flats were filled with Felton loamy sand soil. Since a varietyof grass and broadleaf crops were used in these tests, EPTAM® (EPTC) wasincorporated at 1/2 and 5 lb/A, while a constant rate of 5 lb/A of theadditive was used. EPTAM® (EPTC) and the herbicide additive were appliedseparately by pipetting measured amounts of the appropriate stocksolutions into the soil during incorporation in a 5 gallon rotary cementmixer. Stock solutions for EPTAM were prepared as follows:

A. 1/2 lb/A: 670 mg. of EPTC 6E (75.5% a.i.) was diluted with 500 ml. ofdeionized water so that 2 ml. equals 1/2 lb/A/plastic flat.

B. 5 lb/A: 6700 mg. of EPTC 6E (75.5%) was diluted with 500 ml. ofdeionized water so that 2 ml. equals 5 lb/A/plastic flat.

Additive stock solutions were prepared by diluting 102 mg. of technicalmaterial with 10 ml. of acetone 1% Tween 20® (polyoxyethylene sorbitanmonolaurate) so that 2 ml. equals 5 lb/A/flat.

After the soil was treated with both herbicide and additive, the soilwas transferred from the mixer back into the flat where it was thenprepared for seeding. The initial step in preparation was to remove aone pint sample of soil from each flat to be retained and used to coverthe seeds after planting. The soil was then leveled and rows one-quarterinch deep were made in each flat. Flats treated with 5 lb/A of EPTAMwere seeded to DeKalb XL-44 corn (Zea maize), US H9 sugarbeets (Betavulgare), small seeded gray striped sunflower (Helianthus annus), Acalacotton (Gossypium hirsutum), Brag soybeans (Glycine max) and oilseedrape (Brassica napus), Flats treated with 1/2 lb/A of EPTAM were seededto red oats (Avena byzantina), R-10 milo [sorghum] (Sorghum vulgare),Fremont HRS wheat (Triticum aestivum) , giant foxtail (Seteria feberii),Calrose rice (Oryza sativa) and Blue Mariate barley (Hordeum vulgare).Seeds were then covered with the pint soil sample removed prior toseeding.

The flats were then placed on greenhouse benches where temperatures weremaintained between 70°-90° F. The soil was watered by sprinkling toassure good plant growth.

Injury ratings were taken 2 and 4 weeks after the treatments wereapplied. Soil treated with EPTAM alone at 1/2 or 5 lb/A was included toprovide a basis for determining the amount of injury reduction providedby the herbicide antidotes. The percent protection of variousrepresentative crops is reported in Table III. The per cent protectionis determined by a comparison with flats not treated with the candidateantidote.

                  TABLE III                                                       ______________________________________                                        Multicrop Screen Results                                                      Per Cent Protection                                                           COMPOUND  Rate of               % Protection                                  NUMBER    EPTC lb/A  Crop       (2 weeks)                                     ______________________________________                                        31        0.5        barley     56                                                                 rice       30                                            32        0.5        barley     56                                                                 rice       30                                                      5.0        corn       100                                           33        0.5        rice       30                                                                 barley     44                                            34        0.5        barley     88                                                      5.0        corn       100                                           35        0.5        barley     44                                                      5.0        corn       100                                           36        5.0        corn       100                                           37        5.0        corn       100                                           38        0.5        barley     88                                                      5.0        corn       100                                                     5.0        sunflower  50                                            39        5.0        corn       100                                                     5.0        sunflower  25                                                      5.0        oilseed rape                                                                             60                                            40        5.0        corn       100                                                     5.0        sunflower  25                                            41        0.5        barley     50                                                      5.0        corn       100   (4 weeks)                               42        5.0        corn       56    (4 weeks)                               43        5.0        corn       93    (4 weeks)                               44        5.0        corn       28    (4 weeks)                               45        0.5        barley     50                                                      5.0        sunflower  81                                            46        0.5        rice       100   (4 weeks)                               47        0.5        rice       100   (4 weeks)                                         0.5        barley     75    (4 weeks)                                         5.0        oilseed rape                                                                             68    (4 weeks)                               48        0.5        barley     25                                                      5.0        sunflower  67    (4 weeks)                               49        0.5        sorghum    50                                                      0.5        barley     50                                                      5.0        corn       100   (4 weeks)                               50        5.0        corn       100   (4 weeks)                               51        5.0        corn       42    (4 weeks)                               52        5.0        corn       100   (4 weeks)                               53        0.5        rice       100   (4 weeks)                                         0.5        barley     50    (4 weeks)                                         5.0        corn       70    (4 weeks)                               54        0.5        barley     50                                                      5.0        corn       100   (4 weeks)                               55        0.5        wheat      20    (4 weeks)                                         0.5        barley     100   (4 weeks)                                         5.0        corn       93    (4 weeks)                               56        0.5        sorghum    10    (4 weeks)                               57        0.5        barley     50                                                      5.0        corn       100   (4 weeks)                               58        0.5        rice       100   (4 weeks)                               59        5.0        corn       93    (4 weeks)                               60        0.5        rice       100   (4 weeks)                                         5.0        corn       42    (4 weeks)                               61        0.5        sorghum    40    (4 weeks)                                         0.5        barley     75    (4 weeks)                                         5.0        rice       70    (4 weeks)                               62        5.0        oilseed rape                                                                             65    (4 weeks)                               63        0.5        barley     75                                            64        5.0        corn       42    (4 weeks)                               65        5.0        corn       70    (4 weeks)                               66        5.0        corn       100   (4 weeks)                               67        5.0        corn       28    (4 weeks)                               68        0.5        rice       100   (4 weeks)                                         5.0        corn       93    (4 weeks)                               69        5.0        corn       42    (4 weeks)                               70        5.0        corn       100   (4 weeks)                               71        5.0        corn       70    (4 weeks)                               72        0.5        rice       100   (4 weeks)                                         0.5        barley     50    (4 weeks)                                         5.0        corn       100   (4 weeks)                               73        5.0        corn       100   (4 weeks)                               74        5.0        corn       42    (4 weeks)                               75        0.5        sorghum    71                                                      0.5        wheat      60                                                      5.0        corn       87                                                      5.0        oilseed rape                                                                             71                                            76        5.0        corn       56    (4 weeks)                               77        5.0        corn       100   (4 weeks)                                         5.0        sugarbeets 28    (4 weeks)                               78        0.5        rice       100   (4 weeks)                                         5.0        corn       100   (4 weeks)                                         5.0        sunflower  81    (4 weeks)                               79        0.5        barley     50                                                      5.0        corn       100   (4 weeks)                                         5.0        sunflower  67    (4 weeks)                               80        5.0        corn       70    (4 weeks)                                         5.0        oilseed rape                                                                             56    (4 weeks)                               81        0.5        barley     50    (4 weeks)                                         5.0        sunflower  67    (4 weeks)                               82        5.0        corn       56    (4 weeks)                               83        0.5        rice       100   (4 weeks)                               84        0.5        rice       100   (4 weeks)                                         0.5        barley     50    (4 weeks)                               85        0.5        rice       100   (4 weeks)                                         0.5        barley     75    (4 weeks)                                         5.0        corn       93    (4 weeks)                               86        0.5        barley     50    (4 weeks)                                         5.0        corn       100   (4 weeks)                               87        5.0        corn       93    (4 weeks)                               88        0.5        barley     45                                            89        0.5        wheat      67                                                      5.0        oilseed rape                                                                             75                                            90        0.5        wheat      15                                            91        0.5        sorghum    50                                                      5.0        corn       84                                            92        5.0        oilseed rape                                                                             75                                            93        5.0        oilseed rape                                                                             75                                            94        5.0        oilseed rape                                                                             75                                            95        5.0        oilseed rape                                                                             75                                            96        5.0        corn       80                                            97        0.5        barley     50                                            98        5.0        sunflower  60                                            99        0.5        barley     88                                            100       5.0        corn       100                                           101       5.0        sunflower  100                                           102       5.0        oilseed rape                                                                             50                                            103       0.5        sorghum    30    (4 weeks)                                         5.0        corn       100                                           104       0.5        rice       30    (4 weeks)                                         0.5        sorghum    30    (4 weeks)                               105       0.5        wheat      30    (4 weeks)                                         0.5        barley     75    (4 weeks)                               106       5.0        sunflower  20    (4 weeks)                               107       0.5        wheat      40    (4 weeks)                                         0.5        barley     60    (4 weeks)                                         5.0        corn       100   (4 weeks)                               108       5.0        oilseed rape                                                                             75                                            109       5.0        oilseed rape                                                                             75                                            110       5.0        oilseed rape                                                                             75                                            111       5.0        sunflower  60                                            112       5.0        oilseed rape                                                                             75                                            113       5.0        oilseed rape                                                                             67                                            114       5.0        oilseed rape                                                                             33                                            115       0.5        barley     70    (4 weeks)                                         5.0        corn       10    (4 weeks)                               116       0.5        barley     58    (4 weeks)                                         5.0        sunflower  60    (4 weeks)                                         5.0        corn       100   (4 weeks)                               117       0.5        barley     58    (4 weeks)                                         5.0        corn       100   (4 weeks)                               118       0.5        barley     58    (4 weeks)                                         5.0        corn       65    (4 weeks)                               119       0.5        barley     68    (4 weeks)                                         5.0        corn       100   (4 weeks)                               120       5.0        sunflower  30                                            121       0.5        rice       67    (4 weeks)                                         5.0        oilseed rape                                                                             60    (4 weeks)                               122       0.5        barley     58    (4 weeks)                                         5.0        corn       100   (4 weeks)                               123       0.5        rice       44    (4 weeks)                               124       0.5        rice       67    (4 weeks)                                         0.5        barley     58    (4 weeks)                               125       0.5        rice       88    (4 weeks)                               126       0.5        rice       100                                                     0.5        barley     100                                           127       0.5        rice       78                                                      0.5        barley     64                                            128       0.5        rice       78                                                      0.5        barley     57                                                      5.0        oilseed rape                                                                             60                                            129       0.5        rice       78                                                      0.5        barley     43                                                      5.0        sunflower  100                                           130       0.5        rice       100                                                     0.5        barley     43                                                      5.0        oilseed rape                                                                             40                                                      5.0        soybeans   33                                            131       0.5        barley     43                                                      5.0        sunflower  100                                                     5.0        oilseed rape                                                                             80                                                      5.0        soybeans   47                                            132       0.5        rice       78                                                      0.5        oats       50                                                      0.5        barley     57                                                      5.0        oilseed rape                                                                             100                                                     5.0        corn       58                                            133       0.5        barley     57                                                      0.5        oats       40                                                      5.0        sugarbeets 45                                                      5.0        oilseed rape                                                                             100                                           134       0.5        barley     43                                                      5.0        soybeans   33                                                      5.0        oilseed rape                                                                             80                                            135       0.5        oats       60                                                      5.0        corn       100                                                     5.0        oilseed rape                                                                             100                                           136       0.5        rice       55                                                      0.5        barley     57                                                      5.0        corn       100                                                     5.0        oilseed rape                                                                             80                                            137       0.5        barley     43                                                      0.5        sunflower  70                                                      5.0        soybeans   33                                            138       0.5        rice       78                                                      0.5        barley     71                                                      5.0        oilseed rape                                                                             60                                            139       5.0        sunflower  70                                                      5.0        oilseed rape                                                                             60                                            140       5.0        sunflower  100                                                     5.0        oilseed rape                                                                             60                                                      5.0        soybeans   33                                            141       5.0        soybeans   47                                                      5.0        oilseed rape                                                                             60                                            142       0.5        rice       86                                                      0.5        barley     62.5                                          143       0.5        rice       100                                                     0.5        barley     87.5                                          144       0.5        sorghum    100                                                     0.5        rice       86                                                      0.5        barley     100                                                     5.0        corn       100                                           145       0.5        rice       100                                                     0.5        barley     100                                           146       0.5        barley     75                                                      5.0        oilseed rape                                                                             100                                           147       0.5        rice       72                                                      5.0        corn       88                                            ______________________________________                                    

When used with 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide at 2lb/A, Compounds No. 1 and 30 at 5 lb/A after 4 weeks gave 100 percentprotection to sorghum. Compoun No. 1 also gave 67 percent protection towheat.

When used with 3-(3,4-dichlorophenyl)-1,1-dimethylurea at 1 lb/A,Compounds No. 1 and 30 at 5 lb/A each gave 60 percent protection tocotton; Compound No. 1 also gave 60 percent protection to corn; andCompound No. 30 gave 43 percent protection to corn.

The antidote compounds and compositions of the present invention can beused in any convenient form. Thus, the antidote compounds can beformulated into emulsifiable liquids, emulsifiable concentrates, liquid,wettable powder, powders, granular or any other convenient form. In itspreferred form, a non-phytotoxic quantity of an herbicidal antidotecompound is admixed with a selected herbicide and incorporated into thesoil prior to or after planting the seed. It is to be understood,however, that the herbicides can be incorporated into the soil andthereafter the antidote compound can be incorporated into the soil.Moreover, the crop seed itself can be treated with a non-phytotoxicquantity of the compound and planted into the soil which has beentreated with herbicides, or untreated with the herbicide andsubsequently treated with the herbicide. The addition of the antidotecompound does not affect the herbicidal activity of the herbicides.

The amount of antidote compound present can range between about 0.0001to about 30 parts by weight of antidote compound described herein pereach part by weight of herbicide. The exact amount of antidote compoundwill usually be determined on economic ratios for the most effectiveamount usable. It is understood that a non-phytotoxic quantity ofantidote compound will be employed in the herbicidal compositionsdescribed herein.

The herbicides indicated in the tables and elsewhere are used at rateswhich produce effective control of undesirable vegetation. The range ofrates employed herein produce representative results within therecommended amounts set forth by the supplier. Therefore, the weedcontrol in each instance is commercially acceptable within the desiredor recommended amount.

It is clear that the classes of herbicidal agents described andillustrated herein are characterized as effective herbicides exhibitingsuch activity. The degree of this herbicidal activity varies amongspecific compounds and among combinations of specific compounds withinthe classes. Similarly, the degree of activity to some extent variesamong the species of plants to which a specific herbicidal compound orcombination may be applied. Thus, selection of a specific herbicidalcompound or combination to control undesirable plant species readily maybe made. Within the present invention are prevention of injury to adesired crop species in the presence of a specific compound orcombination may be achieved. The beneficial plant species which can beprotected by this method is not intended to be limited by the specificcrops employed in the examples.

The herbicidal compounds employed in the utility of this invention areactive herbicides of a general type. That is, the members of the classesare herbicidally effective against a wide range of plant species with nodiscrimination between desirable and undesirable species. The method ofcontrolling vegetation comprises applying an herbicidally effectiveamount of the hereindescribed herbicidal compounds to the area or plantlocus where control is desired. The compositions as set forth in thisinvention include those wherein the preferred active herbicidal compoundis selected from EPTC, S-ethyl diisobutyl thiocarbamate, S-propyldipropyl thiocarbamate, S-2,3,3-trichloroallyl-diisopropylthiocarbamate, S-ethyl cyclohexyl ethyl thiocarbamate,2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide, S-ethylhexahydro-1H-azepine-1-carbothioate, 2-chloro-N-isopropylacetanilide,N,N-diallyl-2-chloroacetamide, S-4-chlorobenzyl diethyl thiocarbamate,2-chloro-4-ethylamino-6-isopropylamino-s-triazine,2-chloro-4,6-bis(ethylamino)-s-triazine,2(4-chloro-6-ethylamine-s-triazine-2-yl-amino)-2-methylpropionitrile,2-chloro-4-cyclopropylamino-6-isopropylamino-s-triazine,2,4-dichlorophenoxyacetic acid, its esters and salts, and3-(3,4-dichlorophenyl)-1,1-dimethylurea and combinations thereof.

An herbicide as used herein means a compound which controls or modifiesthe growth of vegetation or plants. Such controlling or modifyingeffects include all deviations from natural development; for example,killing, retardation, defoliation, desiccation, regulation, stunting,tillering, stimulation, dwarfing and the like. By "plants", it is meantgerminant seeds, emerging seedlings, and established vegetation,including the roots and above-ground portions.

What is claimed is:
 1. An herbicidal composition comprising an activeα-halo substituted acetanilide herbicide compound and an antidotetherefor corresponding to the formula ##STR5## in which X is oxygen orsulfur, R is haloalkyl having 1 to 10 carbon atoms, inclusive, and theterm halo includes chloro and bromo substitutions, alkyl having 1 to 10carbon atoms, inclusive, or alkylthio having 1 to 4 carbon atoms,inclusive; R₁, R₂, R₃, R₄, R₅ and R₆ are independently selected from thegroup consisting of hydrogen, lower alkyl having 1 to 4 carbon atoms,inclusive, alkoxyalkyl having a total of 2 to 4 carbon atoms, inclusive,and lower alkylol having 1 to 4 carbon atoms, inclusive; said antidotebeing antidotally active with said α-halo substituted acetanilideherbicide compound.
 2. The composition as set forth in claim 1 wherein Xis oxygen, R is haloalkyl, R₁ is lower alkyl, R₂ is lower alkyl and R₃,R₄, R₅ and R₆ are each hydrogen.
 3. A composition according to claim 2in which R is dichloromethyl, R₁ is methyl and R₂ is methyl.
 4. Acomposition according to claim 2 in which R is monochloromethyl, R₁ ismethyl and R₂ is methyl.
 5. A composition according to claim 2 in whichR is tribromomethyl, R₁ is methyl and R₂ is methyl.
 6. A compositionaccording to claim 2 in which R is monochloromethyl, R₁ is methyl and R₂is ethyl.
 7. A composition according to claim 2 in which R isdichloromethyl, R₁ is methyl and R₂ is ethyl.
 8. A composition accordingto claim 2 in which R is trichloromethyl, R₁ is methyl and R₂ is ethyl.9. A composition according to claim 2 in which R is 1-bromoethyl, R₁ ismethyl and R₂ is ethyl.
 10. A composition according to claim 2 in whichR is tribromomethyl, R₁ is methyl and R₂ is ethyl.
 11. A compositionaccording to claim 2 in which R is monobromomethyl, R₁ is methyl and R₂is ethyl.
 12. A composition according to claim 2 in which R is1,2,4,4-tetrabromopentyl, R₁ is methyl and R₂ is methyl.
 13. Acomposition according to claim 2 in which R is 2-chloroethyl, R₁ ismethyl and R₂ is methyl.
 14. A composition according to claim 2 in whichR is 1,2-dibromoethyl, R₁ is methyl and R₂ is ethyl.
 15. A compositionaccording to claim 2 in which R is 1,2-dibromoethyl, R₁ is methyl and R₂is methyl.
 16. A composition according to claim 2 in which R is1,2-dibromoethyl, R₁ is methyl and R₂ is t-butyl.
 17. A compositionaccording to claim 2 in which R is dichloromethyl, R₁ is methyl and R₂is t-butyl.
 18. A composition according to claim 2 in which R istribromomethyl, R₁ is methyl and R₂ is t-butyl.
 19. A compositionaccording to claim 2 in which R is dichloromethyl, R₁ is methyl and R₂is i-propyl.
 20. A composition according to claim 2 in which R is2-bromoethyl, R₁ is methyl and R₂ is methyl.
 21. A composition accordingto claim 2 in which R is ω-bromodecyl, R₁ is methyl and R₂ is methyl.22. A composition according to claim 2 in which R is 3-chloropropyl, R₁is methyl and R₂ is methyl.
 23. A composition according to claim 2 inwhich R is 2-chloropropyl, R₁ is methyl and R₂ is methyl.
 24. Acomposition according to claim 2 in which R is 1-bromopropyl, R₁ ismethyl and R₂ is methyl.
 25. A composition according to claim 2 in whichR is 1-bromobutyl, R₁ is methyl and R₂ is methyl.
 26. A compositionaccording to claim 2 in which R is 5-bromopentyl, R₁ is methyl and R₂ ismethyl.
 27. A composition according to claim 1 wherein X is oxygen, R isalkyl, R₁ is lower alkyl, R₂ is lower alkyl and R₃, R₄, R₅ and R₆ areeach hydrogen.
 28. A composition according to claim 27 in which R ishexyl, R₁ is methyl and R₂ is methyl.
 29. The composition as set forthin claim 1 wherein X is sulfur, R is haloalkyl, R₁ is lower alkyl, R₂ islower alkyl and R₃, R₄, R₅ and R₆ are each hydrogen.
 30. A compositionaccording to claim 29 in which R is dichloromethyl, R₁ is methyl and R₂is methyl.
 31. A composition according to claim 29 in which R istrichloromethyl, R₁ is methyl and R₂ is methyl.
 32. A compositionaccording to claim 29 in which R is dibromomethyl, R₁ is methyl and R₂is methyl.
 33. A composition according to claim 29 in which R is1-bromoethyl, R₁ is methyl and R₂ is methyl.
 34. A composition accordingto claim 29 in which R is 2-bromoethyl, R₁ is methyl and R₂ is methyl.35. A composition according to claim 29 in which R is 1,2,-dibromoethyl,R₁ is methyl and R₂ is methyl.
 36. A composition according to claim 29in which R is 3-chloropropyl, R₁ is methyl and R₂ is methyl.
 37. Acomposition according to claim 29 in which R is 2-chloropropyl, R₁ ismethyl and R₂ is methyl.
 38. A composition according to claim 29 inwhich R is i-bromopropyl, R₁ is methyl and R₂ is methyl.
 39. Acomposition according to claim 29 in which R is 1-bromobutyl, R₁ ismethyl and R₂ is methyl.
 40. A composition according to claim 29 inwhich R is 5-bromopentyl, R₁ is methyl and R₂ is methyl.
 41. Acomposition according to claim 29 in which R is dichloromethyl, R₁ ismethyl and R₂ is ethyl.
 42. A composition according to claim 29 in whichR is 1-bromoethyl, R₁ is methyl and R₂ is ethyl.
 43. A compositionaccording to claim 29 in which R is 2-bromoethyl, R₁ is methyl and R₂ isethyl.
 44. A composition according to claim 29 in which R ismonochloromethyl, R₁ is methyl and R₂ is ethyl.
 45. The composition asset forth in claim 1 wherein X is oxygen, R is haloalkyl, R₁ is loweralkyl, R₂ is lower alkyl, R₅ is lower alkyl and R₃, R₄, and R₆ are eachhydrogen.
 46. A composition according to claim 45 in which R istribromomethyl, R₁ is methyl, R₂ is methyl and R₅ is methyl.
 47. Acomposition according to claim 45 in which R is monchloromethyl, R₁ ismethyl, R₂ is methyl and R₅ is methyl.
 48. A composition according toclaim 45 in which R is dichloromethyl, R₁ is methyl, R₂ is methyl and R₅is methyl.
 49. A composition according to claim 45 in which R is1-bromoethyl, R₁ is methyl, R₂ is methyl and R₅ is methyl.
 50. Acomposition according to claim 45 in which R is monobromoethyl, R₁ ismethyl, R₂ is methyl and R₅ is methyl.
 51. A composition according toclaim 45 in which R is 1,2-dibromoethyl, R₁ is methyl, R₂ is methyl andR₅ is methyl.
 52. A composition according to claim 45 in which R is2-chloropropyl, R₁ is methyl, R₂ is methyl and R₅ is methyl.
 53. Acomposition according to claim 45 in which R is 1-bromopropyl, R₁ ismethyl, R₂ is methyl and R₅ is methyl.
 54. A composition according toclaim 45 in which R is 1-bromobutyl, R₁ is methyl, R₂ is methyl and R₅is methyl.
 55. A composition according to claim 45 in which R is3-chloropropyl, R₁ is methyl, R₂ is methyl and R₅ is methyl.
 56. Acomposition according to claim 45 in which R is 6-bromopentyl, R₁ ismethyl, R₂ is methyl and R₅ is methyl.
 57. The composition as set forthin claim 1 wherein X is oxygen, R is haloalkyl, R₁ is lower alkyl, R₂ islower alkyl, R₃ is lower alkyl, R₄, R₅ and R₆ are each hydrogen.
 58. Thecomposition as set forth in claim 1 wherein X is oxygen, R is haloalkyl,R₁ is lower alkyl, R₂ is lower alkyl, R₃ is lower alkyl and R₄ is loweralkyl, R₅ and R₆ are each hydrogen.
 59. The composition as set forth inclaim 1 wherein X is oxygen, R is haloalkyl, R₁, R₂, R₃, R₄ and R₅ areeach independently lower alkyl and R₆ is hydrogen.
 60. The compositionas set forth in claim 1 wherein X is oxygen, R is haloalkyl, R₁ isalkoxyalkyl, R₂, R₃, R₄, R₅ and R₆ are each hydrogen.
 61. Thecomposition according to claim 60 in which R is dichloromethyl and R₁ ismethoxymethyl.
 62. The composition as set forth in claim 1 wherein X isoxygen, R is haloalkyl, R₁ is lower alkyl, R₅ is lower alkyl and R₂, R₃,R₄ and R₆ are each hydrogen.
 63. The composition as set forth in claim 1wherein X is oxygen, R is haloalkyl, R₃ is lower alkyl and R₁, R₂, R₄,R₅ and R₆ are each hydrogen.
 64. The composition as set forth in claim 1in which X is oxygen, R is dichloromethyl, R₁, R₂, R₃, R₄, R₅ and R₆ areeach hydrogen.
 65. The composition as set forth in claim 1 in which X issulfur, R is dichloromethyl, R₁ is ethyl, R₂, R₃, R₄, R₅ and R₆ are eachhydrogen.
 66. The method of protecting a grass crop from injury due to aα-halo substituted acetanilide herbicide, comprising applying to thegrass crop seed prior to planting a non-phytotoxic antidotally effectiveamount of a compound corresponding to the formula ##STR6## in which X isoxygen or sulfur, R is haloalkyl having 1 to 10 carbon atoms, inclusive,and the term halo includes chloro and bromo substitutions, alkyl having1 to 10 carbon atoms, inclusive, or alkylthio having 1 to 4 carbonatoms, inclusive; R₁, R₂, R₃, R₄, R₅ and R₆ are independently selectedfrom the group consisting of hydrogen, lower alkyl having 1 to 4 carbonatoms, inclusive, alkoxyalkyl having a total of 2 to 4 carbon atoms,inclusive, and lower alkylol having 1 to 4 carbon atoms, inclusive; saidantidote being antidotally active with said α-halo substitutedacetanilide herbicide compound on said crop.
 67. In the method accordingto claim 66 in which said substituted acetanilide herbicide is2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide and the antidotecompound has the formula wherein R is dichloromethyl, R₁ is methyl, R₂is methyl and R₃, R₄, R₅ and R₆ are each hydrogen.
 68. The method ofprotecting a grass crop from injury due to a α-halo substitutedacetanilide herbicide, comprising preplant incorporation in the soil inwhich said grass crop is to be planted, a non-phytotoxic antidotallyeffective amount of a compound corresponding to the formula ##STR7## inwhich X is oxygen or sulfur, R is haloalkyl having 1 to 10 carbon atoms,inclusive, and the term halo includes chloro and bromo substitutions,alkyl having 1 to 10 carbon atoms, inclusive, or alkylthio having 1 to 4carbon atoms, inclusive; R₁, R₂, R₃, R₄, R₅ and R₆ are independentlyselected from the group consisting of hydrogen, lower alkyl having 1 to4 carbon atoms, inclusive, alkoxyalkyl having a total of 2 to 4 carbonatoms, inclusive, and lower alkylol having 1 to 4 carbon atoms,inclusive, said antidote being antidotally active with said α-halosubstituted acetanilide herbicide compound on said grass crop.
 69. Theherbicidal composition as set forth in claim 1 wherein said activesubstituted acetanilide is selected from the group consisting of2-chloro-2'6'-diethyl-N-(methoxymethyl) acetanilide, and2-chloro-N-isopropyl acetanilide.
 70. The herbicidal composition as setforth in claim 45 wherein an active acetanilide is selected from thegroup consisting of 2-chloro-2'6'-diethyl-N-(methyoxymethyl) acetanilideand 2-chloro-N-isopropyl acetanilide.
 71. The herbicidal compositionaccording to claim 70 in which R is monochloromethyl, R₁ is methyl, R₂is methyl and R₅ is methyl.
 72. The herbicidal composition according toclaim 70 in which R is dichloromethyl, R₁ is methyl, R₂ is methyl and R₅is methyl.
 73. The herbicidal composition according to claim 69 whereinX is oxygen, R is haloalkyl, R₁ is lower alkyl, R₂ is lower alkyl, R₃ islower alkyl, and R₄, R₅ and R₆ are each hydrogen.
 74. The herbicidalcomposition as set forth in claim 69 wherein X is oxygen, R ishaloalkyl, R₁ is lower alkyl, R₂ is lower alkyl, R₃ is lower alkyl, R₄is lower alkyl, and R₅ and R₆ are each hydrogen.
 75. The herbicidalcomposition as set forth in claim 69 wherein X is oxygen, R ishaloalkyl, R₁, R₂, R₃, R₄ and R₅ are each independently lower alkyl, andR₆ is hydrogen.
 76. The herbicidal composition as set forth in claim 69wherein X is oxygen, R is haloalkyl, R₁ is alkoxyalkyl, and R₂ R₃, R₄,R₅ and R₆ are each hydrogen.
 77. The herbicidal composition as set forthin claim 69 wherein X is oxygen, R is haloalkyl, R₁ is lower alkyl, R₅is lower alkyl, and R₂, R₃, R₄ and R₆ are each hydrogen.
 78. Theherbicidal composition as set forth in claim 69 wherein X is oxygen, Ris haloalkyl, R₃ is lower alkyl, and R₁, R₂, R₄, R₅ and R₆ are eachhydrogen.
 79. The method according to claim 66 in which X is oxygen, Ris haloalkyl, R₁ is lower alkyl, R₂ is lower alkyl, R₅ is lower alkyl,and R₃, R₄ and R₆ are each hydrogen.
 80. A composition according toclaim 79 in which R is dichloromethyl, R₁ is methyl, R₂ is methyl, andR₅ is methyl.
 81. The method according to claim 66 in which X is oxygen,R is haloalkyl, R₁ is lower alkyl, R₂ is lower alkyl, R₃ is lower alkyl,and R₄, R₅ and R₆ are each hydrogen.
 82. The method according to claim66 in which X is oxygen, R is haloalkyl, R₁ is lower alkyl, R₂ is loweralkyl, R₃ is lower alkyl, R₄ is lower alkyl, and R₅ and R₆ are eachhydrogen.
 83. The method according to claim 66 in which X is oxygen, Ris haloalkyl, R₁, R₂, R₃, R₄ and R₅ are each independently lower alkyland R₆ is hydrogen.
 84. The method according to claim 66 in which X isoxygen, R is haloalkyl, R₁ is alkoxyalkyl, and R₂, R₃, R₄, R₅ and R₆ areeach hydrogen.
 85. The method according to claim 66 in which X isoxygen, R is haloalkyl, R₁ is lower alkyl, R₅ is lower alkyl, and R₂,R₃, R₄ and R₆ are each hydrogen.
 86. The method according to claim 66 inwhich X is oxygen, R is haloalkyl, R₃ is lower alkyl, and R₁, R₂, R₄, R₅and R₆ are each hydrogen.
 87. The method of protecting a grass plantcrop from injury due to an active α-halo substituted acetanilideherbicidal compound, comprising applying to the soil in which anherbicidally effective amount of said α-halo substituted acetanilideherbicide compound is used, a non-phytotoxic antidotally effectiveamount of a compound corresponding to the formula ##STR8## in which X isoxygen or sulfur, R is haloalkyl having 1 to 10 carbon atoms; inclusive,and the term halo includes chloro and bromo substitutions, alkyl having1 to 10 carbon atoms, inclusive, or alkylthio having 1 to 4 carbonatoms, inclusive; R₁ , R₂, R₃, R₄, R₅ and R₆ are independently selectedfrom the group consisting of hydrogen, lower alkyl having 1 to 4 carbonatoms, inclusive, alkoxyalkyl having a total of 2 to 4 carbon atoms,inclusive, and lower alkylol having 1 to 4 carbon atoms, inclusive; saidantidote being antidotally active with said α-halo substitutedacetanilide herbicide compound on said grass crop.
 88. The methodaccording to claim 87, in which X is oxygen, R is haloalkyl, R₁ is loweralkyl, R₂ is lower alkyl, R₅ is lower alkyl, and R₃, R₄, and R₆ are eachhydrogen.
 89. The method according to claim 88 in which R isdichloromethyl, R₁ is methyl, R₂ is methyl, and R₅ is methyl.
 90. Themethod according to claim 87 in which X is oxygen, R is haloalkyl, R₁ islower alkyl, R₂ is lower alkyl, R₃ is lower alkyl, and R₄ , R₅ and R₆are each hydrogen.
 91. The method according to claim 87 in which X isoxygen, R is haloalkyl, R₁ is lower alkyl, R₂ is lower alkyl, R₃ islower alkyl, R₄ is lower alkyl, and R₅ and R₆ are each hydrogen.
 92. Themethod according to claim 87 in which X is oxygen, R is haloalkyl, R₁,R₂, R₃, R₄ and R₅ are each independently lower alkyl, and R₆ ishydrogen.
 93. The method according to claim 87 in which X is oxygen, Ris haloalkyl, R₁ is alkoxyalkyl, and R₂, R₃, R₄, R₅ and R₆ are eachhydrogen.
 94. The method according to claim 87 in which X is oxygen, Ris haloalkyl, R₁ is lower alkyl, R₅ is lower alkyl, and R₂, R₃, R₄ andR₆ are each hydrogen.
 95. The method according to claim 87 in which X isoxygen, R is haloalkyl, R₃ is lower alkyl, and R₁, R₂, R₄, R₅ and R₆ areeach hydrogen.
 96. The method of protecting a grass plant crop frominjury due to a herbicidally active α-halo substituted acetanilidecompound comprising applying to the soil a herbicidal composition,comprising a herbicidally effective amount of an active α-halosubstituted acetanilide and an antidotally effective amount of anantidote compound having the formula ##STR9## in which X is oxygen orsulfur, R is haloalkyl having 1 to 10 carbon atoms, inclusive, and theterm halo includes chloro and bromo substitutions, alkyl having 1 to 10carbon atoms, inclusive, or alkylthio having 1 to 4 carbon atoms,inclusive; R₁, R₂, R₃, R₄, R₅ and R₆ are independently selected from thegroup consisting of hydrogen, lower alkyl having 1 to 4 carbon atoms,inclusive, alkoxyalkyl having a total of 2 to 4 carbon atoms, inclusive,and lower alkylol having 1 to 4 carbon atoms, inclusive; said antidotebeing antidotally active with said α-halo substituted acetanilideherbicide compound on said grass crop.
 97. The method according to claim96 in which X is oxygen, R is haloalkyl, R₁ is lower alkyl, R₂ is loweralkyl, R₅ is lower alkyl, and R₃, R₄ and R₆ are each hydrogen.
 98. Themethod according to claim 97 in which R is dichloromethyl, R₁ is methyl,R₂ is methyl, and R₅ is methyl.
 99. The method according to claim 96 inwhich X is oxygen, R is haloalkyl, R₁ is lower alkyl, R₂ is lower alkyl,R₃ is lower alkyl, and R₄, R₅ and R₆ are each hydrogen.
 100. The methodaccording to claim 96 in which X is oxygen, R is haloalkyl, R₁ is loweralkyl, R₂ is lower alkyl, R₃ is lower alkyl, R₄ is lower alkyl, and R₅and R₆ are each hydrogen.
 101. The method according to claim 96 in whichX is oxygen, R is haloalkyl, R₁ , R₂, R₃, R₄ and R₅ are eachindependently lower alkyl, and R₆ is hydrogen.
 102. The method accordingto claim 96 in which X is oxygen, R is haloalkyl, R₁ is alkoxyalkyl, andR₂, R₃, R₄, R₅ and R₆ are each hydrogen.
 103. The method according toclaim 96 in which X is oxygen, R is haloalkyl, R₁ is lower alkyl, R₅ islower alkyl, and R₂, R₃, R₄ and R₆ are each hydrogen.
 104. The methodaccording to claim 96 in which X is oxygen, R is haloalkyl, R₃ is loweralkyl, and R₁, R₂, R₄, R₅ and R₆ are each hydrogen.
 105. An herbicidalcomposition according to claim 1 in which the α-halo substitutedacetanilide is α-chloro substituted acetanilide.
 106. The method ofclaim 66 in which α-halo substituted acetanilide is α-chloro substitutedacetanilide.
 107. The method of claim 68 in whith α-halo substitutedacetanilide is α-chloro substituted acetanilide.
 108. The method ofclaim 87 in which α-halo substituted acetanilide is α-chloro substitutedacetanilide.
 109. The method of claim 96 in which α-halo substitutedacetanilide is α-chloro substituted acetanilide.